Herbicidal anilides

ABSTRACT

HERBICIDAL ALMIDOALKYL-E-HALO-SUBSTITUTED ACETANILIDES.

.JKenneth ABSTRACT OF THEv DISCLOSURE Herbicidal amidoalkyl-Z-halo-substituted acetanilides.

' This invention relates to novel amidoalkyl acetanilides which are useful as herbicides and to methods of preparing them. The invention also relates to herbicidal compounds and tomethods of inhibiting or preventing the growth of plant systems.

The term plants is used herein to include germinant seeds, emerging seedlings and established vegetation, including the roots and above-ground portions.

The novel compounds of the present invention are represented by the formula -CHzX 1 wherein:

.R and R are hydrogen, alkyl or alkoxy having at least 1 and not more than carbon atoms and can be like or unlike,

R is hydrogen, alkyl or alkoxy having at least 1 and not more than 10 carbon atoms, N0 or halogen, R .is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylthio, polyalkoxy, polya1kylthio, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl, polyalkylthioalkyl, haloalkyl, fhydroxyalkyl, merc'aptoalkyl, haloalkenyl, oxoalkyl, alkenyloxyalkyl, alkenylthioalkyl, each of a maximum of 18 carbon atoms; cycloalkyl having at least 3 and a maximum of 6 carbon atoms; aryl, aryloxyalkyl, arylthioalkyl, trifluoromethyland haloaryl, trifiuoromethyl and haloaryloxyalkyl, trifluoromethyland haloarylthioalkyl, arylalkyl, nitroaryl, nitroarylthioalkyl, and

nitroarylalkyl having at least 6 and not more than 24 carbon atoms; amino or monoand dialkylamino,

monoarylamino, mono(haloaryl)amino, mono(trifluoromethylaryl)amino, and alkylalkoxyamino having a maximum'of 10 carbon atoms, X is chlorine, bromine or iodine, and n is an integer of'l or 2.

Unlessotherwise indicated, allyl and alkoxy are used generically to include primary, secondary, and tertiary alkyl groups.

Representative compounds of the present invention include those in which the, groups of the above formula have the following identities:

R and R -hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, primary isobutyl, secondary isobutyl, tertiary butyl, n-amyl, branch chain amyls, the normal and branched hexyls, heptyls, octyls, nonyls, and decyls, methoxy, ethoxy, propoxy, butoxy, pentyloxy, heptyloxy, nonyloxy.

R -hydrogen, chlorine, bromine, fluorine, iodine, mtro and the alkyl and alkoxy groups of R and R R hydrogen', methyl, ethyl, propyl, isopropyl, n-butyl, primary isobutyl, secondary, isobutyl, tertiary butyl, the normal and branched amyls, hexyls, heptyls, octyls, nonyls, decyls, dodecyls, tetradecyls, hexadecyls and octadecyls; chloromethly, bromopropyl, iodobutyl, fluorohexyl, hydroxyethyl, dihydroxypropyl; the alk- United States Patent Patented Aug. 20, 1974 oxy, al'kenyl, oxoalkyl, alkoxyalkyl and-alkynyl groups corresponding to the above-enumerated alkyl groups;

phenyl, tolyl, naphthyl, phenoxy, benzyl, phenoxyalkyl; ethylene, trimethylene, tetramethylene; and the like.

The preferred compounds of the present invention are those 1n which both R and R are ethyl and more particularly the compounds in which they are in the ortho posiions.

The novel compounds of the present invention in which n is 1 are prepared by a carbonium ion type reaction of a Z-haIo-N-(substituted methyl) acetanilide with a nitrile or arr inorganic cyanide under acid conditions. The methyl substituent can be any group that is capable of forming a carbomum ion and is readily displaced under acidic conditrons. Thus, the starting material can be a 2-halo-N-methyl acetanilide in which the methyl group is substituted with a halo, alkoxy, alkylthio, hydroxy, mercapto, alkenoyloxy and similar leaving groups. It is particularly preferred, however, to utilize a 2-halo-N-chloromethyl acetanilide 1n the preparation of these compounds. Mineral acids as well as Lewis acids can be employed to provide the acid medium but because of convenience and economics sulfuric acid is generally preferred for this purpose. A solvent can be used but in most instances is not generally required. While the reaction can be conducted at temperatures as low as 0 C., it is generally preferred to accelerate the reaction by conducting it under reflux conditions at the boiling point of the nitrile or solvent in the system. After the reaction is substantially completed the reaction mixture is quenched with water and filtered to recover the acetanilide which may then be purified in any conventional manner.

The 2-halo-N-(substituted methyl)acetanilide used as a starting material in this reaction is the adduct of a haloacetic derivative such as the halide or anhydride with a substituted azomethine or methylenearylamine of the type disclosed and claimed in copending application Ser. No. 625,020, filed Mar. 22, 1967, now abandoned. As more fully described in that application, the azomethines are prepared by the reaction of a suitably substituted aniline with formaldehyde. The 2-halo-N-halomethyl acetanilides that can be employed in preparing the present compounds are described and claimed in copending application, Ser. No. 855,030, filed Sept. 3, 1969, now US. Pat. No. 3,637,- 847.

The compounds of the present invention can also be prepared by reacting a nitrile with an alpha halo-disubstituted- N-(alkoxymethyl)acetanilide of the type described and claimed in US. Pat. 3,442,945, granted May 6, 1969, to John F. Olin.

The novel compounds of the present invention in which n is 2 are readily prepared by the chloroacetylation of an N- (substituted phenyl)-N' acyl ethylenediamine. The ethylenediamine derivatives used as starting materials for such reactions can be readily prepared in conventional manners by the alkylation of a substituted aniline with alkylating agents such as an N-(2-chloroethyl)-alkylamide, N-Z-(hydroxyethyl)-alkylamide or an N-acyl aziridine.

The invention will be more clearly understood by reference to the following detailed description of specific examples thereof. In these examples and throughout the specification, all proportions are expressed in parts by weight unless otherwise indicated.

EXAMPLE 1 This example describes the preparation of 2-chloro-N- (2,6 diethylphenyl)acetamidomethyl chloroacetate. About 168 parts of 2,6 diethylphenyl of azomethine dissolved in benzene were slowly added to about 177 parts of chloroacetic anhydride dissolved in hot benzene. The reaction mixture was agitated until the reaction was sub- This example describes the preparation of 2-chloro-2',

6'-diethyl-N-acetamidomethyl acetanilide. About 80 parts of 2- chloro-N-(2,6'-diethylphenyl)acetamidomethyl chloroacetate prepared in accordance with the general procedure of Example 1 was mixed with about 1000 parts of methyl cyanide and about 2 parts of sulfuric acid in a suitable reaction vessel. The reaction mixture was refluxed for about 2 /2 hours at atmospheric pressure and then poured into a mixture of ice and water. The solid material thus obtained was recrystallized from methanol and melted at 148-149 C.

Calcd for C H ClN O C, 60.7; H, 7.13. Found: C, v

EXAMPLE 3 This example describes the preparation of 2-chloro-2',

6'-diethyl-N-(2,6'- dichlorobenzamidomethyl)acetanilide.1

from the reaction mixture by filtration, washed with water, filtered and recrystallized from toluene to yield a material melting at l50.5l53 C.

'Calcd for C H Cl N O C, 56.16; H, 4.95. Found: C, 55.69; H, 4.85.

EXAMPLE 4 This example describes the preparation of 2-chloro-2, 6-diethyl-N-allylamidomethyl acetanilide About 300 parts of sulfuric acid were charged into a suitable reaction vessel. About 100 parts of 2-chloro-N-chlor0methyl 2',6-diethyl acetanilide and about 26 parts of allyl nitrile, dissolved separately in glacial acetic acid, were added to the sulfuric acid. After these reactants were added, the reaction mixture was heated to about 55 C. for about 15 minutes and then poured into ice water. The resultant solid precipitate was filtered and Washed with water. After recrystallization from isopropanol, the product had a melting point of 121.5l23.5 C.

Calcd for C H ClN O C, 63.25; H, 7.18. Found: C, 62.38; H, 6.95. EXAMPLE 5 This example describes the preparation of 2-chloro-2',

'-diethyl-N-formamidomethyl acetanilide. About 200 parts of 2-chloro-N-chlo-romethyl 2',6'-diethyl acetanilide were added to 400 parts of concentrated sulfuric acid. The mixture was cooled to about 10 C. and 70 parts of sodium cyanide were then added and the reaction mixture heated to about 50 C. The reaction was exothermic and the temperature of the reaction mixture rose to about with a methylcyclohexane-toluene mixture, mp.

Calcd for C H ClN O C, 59246; H, 6.77. .Found:

EXAMPLE 6 This example describes the preparation of 2-chloro-2',

6-diethyl- N (3-chloro-2-methylpropionamidomethyl) acetanilide. About parts of 2-ch1oro-N-chloromethyl 2,6'-diethyl acetanilide were mixed with 26 parts of methac'ryl'oriitrile and add'd to "'ab6i1t'35'0 partssulfurieac'id at a temperature of about; 10 C. in a suitable reaction vessel. The reaction mixturewas heated to about 65 C. for about four hours while 'dry.. hydrogen chloride gas was ubbled through '"it. I he re'acti'orimixture waspoured into ice water and filtered itQ remOve ,thepr'ecipit'atewhich wa-s then recrystallized from isop ropanol....,.]Q. 1

Calcd for C H Clg-NgO' z 0,356.83; H, 6.73. Found: C, 56.85; H, 6.62. L; 1].. EX M Z EZ.

This example des'cribesthe preparat'ion of"-2-chloro-2'- 6'-diethyl-N-acrylamidomethyl' acetanilide,About; parts of 2-chloro-2,6GdiethyLNemethoxymethyl acetanilide were mixed with about 27 parts of acrylonitrile and about 300 parts of sulfuric acid wereadded. The reaction mixture was heated to about 55 C. and maintained. at that temperature for about one hour. At .theend of that time the reaction mixture was poured into. ice' wateran'd yielded a solid granular precipitate. This material was removed from the reaction-mixture by filtration, washed with water and recrystallized from isop'ropanol. Therecrystallized material melted at. l74 -l 7 5 C. Y

Calcd for C H CIN O C, 6 2.23; H, 6.85. Found: C, 62.54; H, 7.05.

EXAMPLE 8 This example describes the preparation of 2-chloro-2'- ethyl-6'-methyl-N (cyclopropane carboxamidomethyl) acetanilide. 'About 300 parts of concentrated sulfuric acid were charged into a suitable reaction vessel and cooled to about 0 C. while being agitated. About-100 parts of 2-chloro-2'-ethyl-6'-methyl-N-chloromethyl acetanilide were slowly added and the,mixtu're heated --to about 25 C. to expedite dissolution of the adduct, The mixture was again cooled to about 10 C. and about 28 parts of cyclopropyl nitrile were slowly added. After the addition of the nitrile was completed, the" reaction inixture was heated to about 55 C for about"20' minutes and then poured into ice water. This resulted in: the formation of a gummy precipitate which solidified upon standing about 8 hours- The solid precipitatae was separated by filtration, washed with water, filtered. and recrystallized from isopropanol. This material melted at 154156.5 C.

EXAMPLES '9 THROUGH 48 The following compounds are also prepared by substantial repetition of the general procedures set forth in the foregoing examples: 1

(9) 2-chloro-2,6'-diethyl N- (cinnanlamidomethyl) acetanilide I V (10) 2-chl oro-2,6'-diisopropyl-N (butyramidomethyl) acetanilide 1 1) 2-bromo-2,3',6'-trimethyl-N-(ace'tamidomethyl) acetanilide v i I l2) 2-iodo-2,6-diethyl-4'-methyl-N- (chloroacetamidomethyl)acetanilide f (l3) 2-chl0ro-2',6'-die'thyl-N- 3ethoxypropionamidomethyl)acetanilide (14) 2-chloro-2,6'-diethyl-N-(2-ch1oroacetamido methyl)acetanilide p -11, (15 2-chloro-2',6'-diethyl-N-isobutylamidomethyl)acetanilide 1 g (16) 2-chloro-2,6GdiethyLN-caprylamidomethyl.'

acetanilide (l7) 2-chl'oro-2,6-diethyl-N-j(beta-chloropropionamidomethyl)acetanilide r i (18) 2-chloro-2,6-diethyl-Npropionamidomethylacetanilide (19) 2-chloro-2',6-diethylvN-butyramidonrethyl acetanilide 20 2 -chloro -2',6'-diethyl-N-oxamidomethyl acetanilide are represented by letters I-Hemp Sesbania J-Lambs-quarters K-Velvetleaf LBromus tectorum M-Panicum spp. N-Barnyard grass OCrabgrass Plant species (47) 2-chloro-2,6'-diethyl-N-(cinnamarnidoethyl) acetanilide (48) 2-chloro-2',6'-diisopropyl-N-(butyramidoethyl)acetanilide. v

5 I In order to illustrate the, advantages of the present invention, the pre-emergence herbicidal ratings of representative 2-haloacetanilides were determined in greenhouse tests in which a specific number of seeds of a number of difierent plants, each representing a principal botanical type, were planted in greenhouse 'flats. v

p A good grade of top soil was placed inaluminumpans and compacted to adepth of to inch from the top of the pan. On the top of the soil was placed a predetermined number of seeds of various plant species. In the surface application the seeds were covered by overfilling the pan with soil and striking it level. The measured amount of chemical in a suitable solvent or as a wettable powder was applied to this surface. In the soil incorporation treatments the soil required to level fill pans after seeding was weighed into a pan, a known amount of the chemical applied in a solvent or as a wettable powder, the soil thoroughly mixed, and used as a cover layer for seeded pans. After treatment the pans were moved into a greenhouse bench where they were watered from below as needed to give adequate moisture for germination and growth.

Approximately 14 days after seeding and treating, the plants were observed and the results recorded. The herbicidal rating was obtained by means of a fixed scale based on the average percent germination of each seed lot. The ratings are defined as follows: 0No herbicidal activity 1Slight herbicidal activity 2Moderate herbicidal activity 3Severe herbicidal activity.

The pre-emergence herbicidal activity of the alphahaloacetanilides are recorded in the following table for various application rates in both surface and soil-incorporated applications.

-In the table, the letter M following the rate of application indicates that the herbicide was incorporated in the soil and the various seeds as follows:

A-Soybean B-Sugar beet CWheat D-Rice E-Sorghum F-Cocklebur (common) GWi1d buckwheat HMorning glory PRE-EMERGENCE HERBICIDAL ACTIVITY Rate, 1b./a.ABCDE FGH I JKLMN 0 (21) 2-chloro-2'56'-diethyl-N-ureid0methy1 acetanilide f v (22) 2-chloro-2',6'-diethyl-N-benzamidomethyl p acetanilide 3 v (23 Z-chloro-2f,6-diethyl-N-phenylacetamidomethyl) acetanilide (24) 2-chloro-ZQ6'-diethyl-N-methacrylamidomethyUacetanilide H (25 2-chloro-2f,6'-diethyl-N-(3-ethylthiopropionamidomethyDacetanilide (26) 2-chloro-2',6'-diethyl-N-lauramidomethyl acetanilide i I (27) 2-bromo-2,6-dimethyl-N-urethylanylmethyl acetanilide (28) 2-chloro-2'-tert-butyl-N-valeramidomethyl acetanilide I methyl)acetanilide (30) 2-chloro-2 ',6'-diethyl-N-(1,2-dichloropropionamidomethyl)acetanilide f 3 1) 2-chloro-2,6'-diethyl-N- (mthacrylamidomethyl) acetanilide (32) 2-chloro-2'-methyl-6-tertiary butyl-N-(methacrylamidomethyl)acetanilide (33) 2-chloro-2'-methoxy-6-tertiary butyl-N-(methacrylami domethyl) acetanilide (34) 2-chloro-2',6-dimethyl-N-(methacrylamidop methyDacetanilide v (35) 2-chloro-2',3'-dimethyl-6'-tertiary butyl-N-(acetamidomethyl)acetanilide (36) 2-bromo-2-methyl-6'-tertiary butyl-N-(methacrylamidomethyl) acetanilide (37) 2-chloro-2',6'-diethyl-N-(cyclopropane carboxamidomethyl) acetanilide (38) 2-chloro-2',6-diethy1-N-(3-methoxypropionamidomethyl)acetanilide (39) 2-bromo-2-ethyl-6'-tertiary butyl-N-(acetamidomethyl) acetanilide (40) 2-chloro-2',6T-diethyl-N-acetamidoethyl acetanilide (41) 2-chloro-2',6 '-diethyl-N-(2",6-dichlorobenzamidoethyl) acetanilide (42) 2-chloro-2',6'qdiethyl-N-allylamidoethyl acetanilide (43) 2-chloro-2',6'-diethyl-N-formamidoethyl acetanilide v (44) 2-chloro-2-,6'-diethyl-N-(3-chloro-2-methylpropionamidoethyl)acetanilide (45) 2-chloro 2',6'-diethyl-N-acrylamidoethyl acetanilide (46) 2-chloro-2-ethyl-6'-methyl-N-(cyclopropane carboxamidoethyl) ac etanilide Compound of Example No.

m m am fl m xummmnMMxmx o 1 f IaS p sense The data set forththetforegoing tableclearly illustrates that the compounds oft'he'present' invention are effective herbicides and are particularly useful in the control of narrow leaf or grass weeds, even in the presence liquid for solid forrriJThe. compositions are preparedby admixing 'the' active ingredient with an adjuvant. including J diluents, extenders, carriers and eonditioning agents to j fp rovi e compositions in the for mfof finj ely-divided pap "t'i'culate solids, granules, pellets,'s'olutio'ns, dispersions or emulsions. Thus the active ingredient can be used with an adjuvant such as finely divided solid, a liquid of organic origin, water, a Wetting agent, a dispersing agent, an

emulsifying agent or any suitable combination of these.

The compositions of this invention, particularly liquids and wettable powders, preferably contain as a conditioning agent one or more surface-active agents in amounts r sufficient to render 'a given composition readily dispersible in water or oil. The incorporation of a surface-active agent into the compositions greatly enhances their efficacy. By the term surface-active agent it is understood that wetting agents, dispersing agents, suspendingagents and emulsifying agents are included therein. Anionic, cationic and non-ionic agents can be used with equal facility.

Preferred wetting agents are alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isethionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, polyoxyethylene derivatives of alkylphenols (particularly isooctylphe- I101 and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides (e.g. sorbitan) Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium napthalene sulfonate, 40

and polymethylene bisnaphthalenesulfonate.

Wettable powders are water-dispersible compositions containing one or more active ingredients, an inert solid extender and one or more Wetting and dispersing agents.

The inert solid extenders are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powder compositions of this invention usually contain from about 5 to about 95 parts of active ingredient, from about 0.25 to 25 parts of wetting agent, from about 0.25 to 25 parts of dispersant and from 4.5 to about 94.5 parts of inert solid extender, all parts being by Weight of the total composition. Where required, from about 0.1 to 2.0 parts of the solid inert extender can be replaced by a corrosion in hibitor or anti-foaming agent or both.

Aqueous suspensions can be prepared by mixing toa gether and grinding an aqueous slurry of water-insoluble ticles. The resulting concentrated aqueous suspension is.

active ingredient in the presence of dispersing agents to 0.

obtain a concentrated slurry of very finely-divided par- I characterized by its extremely small particle; size, so that .v when diluted and sprayed, coverage is very uniform;-

Emulsifiable ,oils' are usually solutions of active in- 1 gredient in water-immisciblej-or par tially water-immiscible I} weight of'emulsifiable oil.

tain from about 5 to parts active ingredient, about 1 to 50 parts surface active agent and about 4 to; 94 parts solvent, all parts being by Weight based on the total" Granules arephysicallyfstable particulate compositions comprising active 'ing'redient'adher'ing to or distributed through abasicmatrix of an inert, finely-divided particulate extender. In 'or d er'to aid leaching of the active ingredient from the, part icul z 1t e .,v a surface active agent such as those listed hereinbefore can -be i'esent he' 'c 'omposition. Natural clays, pyrophyllites, ill t' and y rnicu'lite are examples of operable classes of particulate mineral extenders, The preferred extendersare 'the' 'p'o us, .abSprptive, performed particles'sucfias'perfornied slcreened particulate attapulgite or heat expanded;'particulatelvcrmiculite, and the finely-divided clays such as kaolin clays, hydrated attapulgite or bentonitic clays. Thes" extenders are sprayed or blendedwith the active ingredient to form the herbicidal granules. f

The granular compositions of this invention generally contain from about 5 parts to about 30 partsby weight of active ingredient per parts by weight of clay and O to about 5 parts by weight of surface active agent per '100 parts by weight of particulate clay. The preferred gra'nular compositions contain from about loparts to about 25 parts by weight of active ingredient per 100 parts by weight of clay. I

The compositions of this invention can also contain other additaments, for example" fertilizers, herbicides, other pesticides and "the like used as adjuvants "or in combination with any of the "above-described adjuvants. Chemicals useful in combination with the active ingredients of .this invention include for example triazines, ureas, ca'rbamates, acetamides, acetanilides, uracils, acetic acids, phenols, thiolcarbamates, tria'zole's, benzoic acids, 'n'itriles and the like such as:

3-arnino-2,S-dichlorobenzoic' acid 3-amino-1,2,4-triazole I 2-methoxy-4-ethylamin'o-6-isopropylaniino-s-triazine 2-chloro-4-ethylamino-6-isopropylamino-s-triazine' 2-chloro-N,N-diallylacetamide 2-chloroallyl diethyldithiocarbamate' N'-(4-chlorophenoxy)phenyl-N,N-dimethylurea 1,l'-dimethyl-4,4-bipyridinium dichloride isopropyl N-(3-chlorophenyl)carbamate 2,2-dichloropropionic acid I S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate- 2-methoxy-3,fi-dichlorobenzoic acid 2,6-dichlorobenzonitrile N,N-dimethyl-2,2-diphenylacetamide 6,7-dihydrodipyrido( 1 ,2-a: 2", l '-c) -pyra'zidiinium salt 3-(3,4dichlorophenyl)-l,l-dimethylure 4 4,6-dinitro-0-sec-butylphenol Z-methyl-4,6-dinitropheno1 ethyl N,N-dipropylthio1carb amate- 2,3,6-trichlorophenylacetic acid 5-bromo-3-isopropyl-6-methyluracil 3'-( 3 ,4-dich1orophenyl l-methoxy- 1 -methylurea 2-methyl-4-chlorophenoxyacetic acid 3(p-chlorophenyl)-1,1-dimethylurea 1-butyl-3- 3,4-dichlorophenyl l-methylurea N -l-naphthylphthalamic acid 1,1 '-ditnethyl-4,4-bipyridinium salt 2-chloro-4,6-bis(isopropylamino)-s-triazine 2-chloro-4,6-bis (ethylamino) -s-triazine 2,4-dichlorophenyl-4-nitrophenyl ether alpha, alpha, alpha-trifluoro-2,6-dinitro-N,N-dipropylp-toluidine S -pr'opyl dipropylthiolcarbamate 2,4-dichlorophenoxyacetic acid N-jisolaropyl-Z-chloroacetanilide 2,6'1diethyl-N-methoxymethyl-2-chloroacetanilide mono sodium acid methanearsonate 0 disodiuin methanecarsonate N- ('1, lidimethylpropynyl -3,5-dichlorobenzamide.

and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

When operating in accordance with the present invention, effective amounts of the acetanilides are applied to the plants, or to soil containing the plants, or are incorporated into aquatic media in any convenient fashion. The application of liquid and particulate solid compositions to plants or soil can be carried out by conventional methods, e.g. power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages. The application of herbicidal compositions to aquatic plants is usually carried out by adding the compositions to the aquatic media in the area where control of the aquatic plants is desired.

The application of an effective amount of the compounds of this invention to the plant is essential and critical for the practice of the present invention. The exact amount of active ingredient to be employed is dependent upon various factors, including the plant species and stage of development thereof, the type and condition of soil, the amount of rainfall and the specific acetanilide employed. In non-selective pre-emergence treatments, the compounds of this invention are usually applied at an approximate rate of from 1 to 25 pounds per acre. In selective pre-emergence application to the plants or to the soil containing a dosage of from 0.05 to about 5 pounds of acetanilide per acre is usually employed. Lower or higher rates may be required in some instances. One skilled in the art can readily determine from this specification, including the examples, the optimum rate to be applied in any particular case.

The term soil is employed in its broadest sense to be inclusive of all conventional soils as defined in Websters New International Dictionary, Second Edition, Unabridged (1961). Thus the term refers to any substance or media in which vegetation may take root and grow, and includes not only earth but also compost, manure, muck, humus, sand and the like, adapted to support plant growth.

Although the invention is described with respect to specific modifications, the details thereof are not to be construed as limitations except to the extent indicated in the following claims.

What is claimed is:

1. A compound of the formula ("J-CHzX 10 wherein:

R and R are selected from the group consisting of hydrogen, alkyl and alkoxy having at least 1 and not more than 10 carbon atoms;

R is selected from the group consisting of hydrogen, alkyl and alkoxy having at least 1 and not more than 10 carbon atoms, N0 and halogen;

R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, each having a maximum of 18 carbon atoms; cycloalkyl having a maximum of 6 carbon atoms, phenyl, dichlorophenyl, tolyl, naphthyl, benzyl, cinnamyl, phenoxy and amine;

X is chlorine, bromine or iodine; and

n is an integer of 1 or 2.

2. A compound of Claim 1 wherein R and R are alkyl and are in the 2 and 6 positions.

3. A compound of Claim 2 wherein R and R are ethyl.

4. A compound of Claim 3 wherein R is alkyl.

5. A compound of Claim 1 wherein n is 1.

6. A compound of Claim 2 which is 2 chloro-2',6'-

diethyl N acetamidomethyl acetanilide.

7. A compound of Claim 2 which is 2-chloro-2,6'-diethyl-N-(cyclopropane carboxamidomethyl) acetanilide,

8. A compound of Claim 2 which is 2 chloro 2'- methyl-6-ethyl N (acetamidomethyl) acetanilide.

9. A compound of Claim 2 which is 2-chloro-2',6-diethyl N (beta-chloropropionamidomethyl)-acetanilide.

References Cited UNITED STATES PATENTS 2,719,176 9/1955 Coover et al. 260-561 2,628,217 2/1953 Magat 260561 2,518,156 8/1950 Magat 260-561 OTHER REFERENCES Krimen et al.: Organic Reactions, vol. 17, pp. 213- (1969).

HARRY I. MOATZ, Primary Examiner US. Cl. X.R.

71-98, 118, 120, 107; 260471 C, 553 A, 558 D, 562 B 

